(1) Field of the Invention
This invention relates to a novel-infrared absorbent for absorbing near infrared rays having a wavelength of 700-1500 nm or for absorbing a far infrared rays which scarcely interfere with the transmission of visible light.
(2) Description of the Prior Art
Heretofore, various applications of an infrared absorbing material capable of selectively absorbing rays of far infrared light or of near infrared light having a wavelength of 700-1500 nm have been proposed. The following five examples show conventional primary applications of an infrared absorbing material.
(1) Safelight filter for infrared-sensitive materials:
Recently, there have been developed many silver halide light sensitive materials (which will be hereinafter referred to as "light sensitive materials") which are sensitive to rays of far infrared light or near infrared light having a wavelength of 700 nm or more. That is, light sensitive materials are made to have an infrared sensitivity irrespective of any distinction between black and white photographs or color photographs including a normal-type, instant-type and thermal developed-type photographs. These filter materials are useful for an artificial color photograph for a resource search or they may be used or exposed with a light emission diode capable of emitting a light in an infrared area.
Conventionally, a safelight filter for a panchromatic photosensitive material has been used for such infrared-sensitive materials.
(2) Control of the growth of plants:
It has been long known that a so-called morphogenesis with regard to growth and differentiation of plants such as germination of seed, extension of stem, development of leaf, budding of flower and formation of tuber is influenced by a light, and it has been studied as a photomorphogenesis. It is also known that a red light having a wavelength of about 660 nm and a red light having a wavelength of about 720-730 nm antagonistically function to each other, and therefore the time of flowering or earing, or the extent of growth or yield of fruits can be varied by changing a proportion of both types of light. Such a study has been made by controlling a spectral energy distribution of a light source lamp and a filter in combination. Therefore, it was difficult to carry out a test in a large-scale green house or farm.
If a plastic film capable of selectively absorbing rays having a wavelength of 700 nm or more is obtainable, it will be possible to control a spectral energy distribution of light to adapt the above-mentioned principle to an actual productive cite, thereby providing great progress and profit to aggricultural equipment. For example, it is expected that earing time may be delayed or growth may be controlled by covering plants with a near-infrared absorbing film at a specific time to cut-off a light having a wavelength of 700 nm or more. (See "Chemical Control of Plants", Katsumi Ineda, Vol. 6, No. 1 (1971))
(3) Cut-off of heat radiation:
Solar radient energy rays of near infrared and infrared areas having a wavelength of 800 nm or more are absorbed by an object and converted to a thermal energy. In addition, a large part of its energy distribution is converged at a near infrared area having a wavelength of 800-2000 nm. Accordingly, a film capable of selectively absorbing rays of a near infrared light is remarkably effective for the cut-off of solar energy, and it is possible to suppress an increase in temperature in a room admitting visible light. Such a film may be adapted to a window of a house, office, store, automobile and airplane, etc. as well as a gardening green house. In particular, in a green house, temperature control is very important and if the temperature is excessively elevated, the plants will be greatly damaged causing them to wither. Accordingly, when the near infrared absorbing film is used, the temperature control may be rendered easy, and a new technique such as retarded cultivation in summer may be developed. A conventional heat radiation cutting-off material includes a thin metallic layer deposited on a surface of a plastic film or an inorganic compound, e.g., FeO dispersed in a glass.
(4) Cut filter of infrared rays harmful to tissues of human eyes:
Infrared rays contained in sun light or in light radiated in welding have a harmful influence to the tissues of human eyes. One of the primary applications of the infrared cut filter is an application to spectacles for protecting the human eyes from rays of light containing such harmful infrared rays, e.g., sunglasses and protecting glasses in welding.
(5) Infrared cut filter for semiconductor light receiving element:
In another field where development of this kind of infrared absorbing plastics is most intensively desired, the infrared absorbing plastics are adapted to an infrared cut filter for a photosensor to make the spectral sensitivity of a semiconductor light receiving element such as silicon photo diode (which will be hereinafter referred to as SPD) approach the relative spectral sensitivity curve.
Presently, SPD is mainly used as a light receiving element of a photosensor used in an automatic exposure meter for a camera or the like. FIG. 2 shows a graph of the relative spectral sensitivity curve and that of a relative value of an output of SPD to each wavelength.
In order to use SPD for an exposure meter, it is required to cut-off light in an infrared area which is not sensitive to human eyes and to make the spectral sensitivity curve of SPD shown in FIG. 2 approach the relative spectral sensitivity curve. Particularly, as an output of SPD is large with light having a wavelength of 700-1100 nm, and the eyes are insensitive to such light, this is one of the factors for the malfunctioning of the exposure meter. Therefore, if it is possible to use an infrared absorbing plastic film suppressing an absorption of a visible light area, while permitting an absorption of an infrared light area in the entire range of 700-1100 nm, the light transmittance in a visible area may be increased and an output of SPD may be also increased. Thus, it will be possible to apparently remarkably improve the performance of the exposure meter.
Conventionally, this kind of photosensor has been particularly used by mounting an infrared cut filter made of glass containing an inorganic infrared absorbent to a front surface of SPD.
Moreover, in general organic dyestuff infrared absorbents of the prior art are unsatisfactory in practical use because of their low light fastness and heat fastness.
Further, regarding the above-mentioned applications, filter materials as previously used have the following shortcomings.
The safelight filter for the panchromic photosensitive material in the afore-mentioned applications (1) permits green light having a high luminosity factor to be partially transmitted, and also permits a large quantity of infrared light to be transmitted to cause fogging. For this reason, such a safelight filter has not been able to achieve its object for infrared sensitive materials.
In the applications in (3), the metallic layer deposited plastic film or the FeO dispersed glass functions to intensively absorb not only infrared light but also visible light to cause reduction in inside luminance. For this reason, such a plastic film or glass is not suitable for agricultural uses because of the lack of an absolute quantity of sunshine. Especially, the filter material for the growth control of plants in the applications in (2) is required to selectively absorb a light having a wavelength of 700-750 nm, and therefore the metallic layer deposited film is quite unsuitable for such an object.
Furthermore, in the applications in (5), the infrared cut filter using the infrared absorbent containing an inorganic substance is relatively fast to heat and light, but light transmittance in a visible area is low. To cope with this, the sensitivity of SPD was intended to be increased. However, an increase in the sensitivity of SPD results in an increase in the leak current which causes a malfunction of the photosensor, resulting in a big problem in reliability. Additionally, since the infrared cut filter contains an inorganic substance, there is a lack in the flexibility in production of a photosensor and a difficulty in improving the production process. Further, the infrared cut filter containing an inorganic substance causes a high production cost which results in a great increase in the cost of the photosensor.
In this manner, although the photosensor using the conventional cut filter containing an inorganic substance has a spectral sensitivity similar to the spectral luminous efficiency curve, it has a remarkable defect in such a viewpoint as the reduction in an operational performance, increase in the production cost and difficulty in improving the production process.
Moreover, the conventional near-infrared absorbing plastic film containing the infrared absorbent of a complex containing qauternary ammonium group does not have sufficient solubility of the infrared absorbent in an organic solvent, which was a restriction in preparing a thin plastic film layer.
In other words, the SPD filter as mentioned above is desired to have a much smaller thickness and a good absorption efficiency of infrared rays. To this end, it is necessary to disperse a large quantity of infrared absorbent in resin. Therefore, the infrared absorbent having a small solubility in an organic solvent has not met the above requirements.
Furthermore, a conventional near-infrared absorbing plastic film containing a metal complex as an infrared absorbent has a short wavelength or absorption maximum, and therefore it was unsuitable for application in a light receiving element of a semiconductor laser which is increasing its uses.